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• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/06—Polyethene
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  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F10/02—Ethene
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/28—Treatment by wave energy or particle radiation
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
  • C08F2500/04—Broad molecular weight distribution, i.e. Mw/Mn > 6
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
  • C08F2500/12—Melt flow index or melt flow ratio
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2323/04—Homopolymers or copolymers of ethene
  • C08J2323/06—Polyethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/14—Applications used for foams
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/16—Applications used for films
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/30—Applications used for thermoforming
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2207/00—Properties characterising the ingredient of the composition
  • C08L2207/06—Properties of polyethylene
  • C08L2207/062—HDPE
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2207/00—Properties characterising the ingredient of the composition
  • C08L2207/06—Properties of polyethylene
  • C08L2207/066—LDPE (radical process)

Definitions

• This disclosure relates to low density polyethylene resins and processes to modify them to improve their physical properties.
• LDPE Low density polyethylene
• LDPE resins are ethylene polymers prepared using a free-radical, high pressure ( ⁇ 100 MPa (for example, 100-400 MPa)) polymerization.
• LDPE resins typically have a density in the range of 0.915 to 0.935 g/cm 3 .
• an agitated autoclave vessel having one or more reaction zones is used.
• the autoclave reactor normally has several injection points for initiator or monomer feeds, or both.
• a jacketed tube is used as a tubular reactor, which has one or more reaction zones. Suitable, but not limiting, reactor lengths may be from 100 to 3000 meters (m), or from 1000 to 2000 m.
• the beginning of a reaction zone for the reactor is typically defined by the side injection of either initiator of the reaction, ethylene, chain transfer agent (or telomer), comonomer(s), as well as any combination thereof.
• a high pressure process can also be carried out in autoclave or tubular reactors having one or more reaction zones, or in a combination of autoclave and tubular reactors, each comprising one or more reaction zones.
• a chain transfer agent can be used to control molecular weight.
• one or more chain transfer agents may be added to a polymerization process.
• Typical CTAs include, but are not limited to, propylene, isobutane, n-butane, 1-butene, methyl ethyl ketone, acetone, and propionaldehyde.
• LDPE resins are used in many conventional thermoplastic fabrication processes to produce useful articles, including monolayer and multilayer films; molded articles, such as blow molded, injection molded, cast molded, or rotomolded articles; coatings; fibers; and woven or non-woven fabrics.
• the films include extrusion coatings, food packaging, consumer, industrial, agricultural (applications or films), lamination films, fresh cut produce films, cast films, blown films, thermoformed films, meat films, cheese films, candy films, clarity shrink films, collation shrink films, stretch films, silage films, greenhouse films, fumigation films, liner films, stretch hood, heavy duty shipping sacks, pet food, sandwich bags, sealants, and diaper backsheets.
• LDPE resins may also be used in wire and cable coating operations, in sheet extrusion for vacuum forming operations, and forming molded articles, including the use of injection molding, blow molding, or rotomolding processes, in soft touch goods, such as appliance handles, in gaskets and profiles, in auto interior parts and profiles, in foam goods (both open and closed cell) and as impact modifiers for other thermoplastic polymers, such as high density polyethylene.
• LDPE resins that are used in these applications desirably have high melt strength, high shear thinning and relatively low melt index in order to provide good processability.
• LDPE typically adds flexibility and processability to the blend, while HDPE or LLDPE adds rigidity and strength.
• Blending LDPE with linear low density polyethylene increases bubble stability, in part due to the higher melt strength of the LDPE.
• An LDPE resin that has higher melt strength can be used in smaller quantities in the extruded blend and/or can allow faster film production.
• too high of a melt strength can cause gels and poor quality film.
• some high melt-strength LDPE resins frequently have low melt index and little shear thinning, which makes them harder to process.
• new ethylene-based polymers such as LDPEs, that have an optimized balance of melt strength, melt index and rheological properties.
• post-treatment methods are known to induce cross-linking or formation of long-chain branches in polyethylenes (HDPE, LLDPE and LDPE).
• Examples of known post-treatment techniques include treatment with oxygen, free-radical initiators, high-energy electromagnetic radiation and electron beams. Examples of post-treatment technology are described in the following US patents and patent applications: U.S. Pat. Nos. 4,586,995; 7,094,472 B2; U.S. Pat. No. 7,892,446 B2; U.S. Pat. No.
• LDPE low-density polyethylene
• One embodiment of the present invention is a process to modify an LDPE resin, which process comprises the steps of:
• a third embodiment of the present invention is a manufactured article comprising the modified polyethylene formulation.
• This application describes several characteristics of the starting LDPE resins and modified LDPE resins, such as density, melt index, conventional and absolute molecular weights, and various branching and rheology measurements.
• the characteristics described are measured by the test methods listed in the “Test Methods” section of this application. Reference to a measured characteristic should be taken as meaning the characteristic as measured by the listed test method. Alternative test methods may sometimes yield different results.
• a starting LDPE resin is subjected to electron beam radiation.
• the starting LDPE resin and the modified LDPE resin in this invention are polyethylene polymers.
• polymer refers to a polymeric compound prepared by polymerizing monomers, whether of the same or a different type.
• the generic term polymer thus embraces both homopolymers and interpolymers as defined hereinafter.
• Polyethylene homopolymers contain repeating units derived almost exclusively from ethylene, with the understanding that low amounts of impurities such as chain transfer agents can be incorporated into the polymer structure.
• the impurities preferably make up less than 1 weight percent of the homopolymer, more preferably less than 0.5 weight percent and most preferably less than 0.3 weight percent.
• Polyethylene interpolymers are polymers prepared by the polymerization of ethylene monomer with at least one different type of monomer.
• the generic term interpolymer includes ethylene copolymers (employed to refer to polymers prepared from ethylene and one other comonomer), and polymers prepared from ethylene and two or more comonomers.
• Polyethylene interpolymers may also contain low amounts of impurities such as chain transfer agents which can be incorporated into the polymer structure.
• preferably at least 50 weight percent of repeating units are derived from ethylene monomer.
• the starting LDPE resins and modified LDPE resins are more preferably ethylene homopolymers.
• the starting LDPE resin has the following characteristics: (i) a density from 0.91 g/cm 3 to 0.94 g/cm 3 ; (ii) a melt-index (I 2 ) from 5 to 18 dg/min; and (iii) a conventional molecular weight distribution (M w (Conv) /M n (Conv) ) of at least 6.
• the density of the starting LDPE resin is from 0.91 g/cm 3 to 0.94 g/cm 3 .
• the density of the starting LDPE resin is preferably at least 0.912 g/cm 3 , more preferably at least 0.915 g/cm 3 and most preferably at least 0.917 g/cm 3 .
• the density of the starting LDPE resin is preferably at most 0.935 g/cm 3 , more preferably at most 0.930 g/cm 3 and most preferably at most 0.925 g/cm 3 .
• the melt index (I 2 ) of the starting LDPE resin component ranges from 5 dg/min to 18 dg/min.
• the melt index is preferably at least 6 dg/min, more preferably at least 6.5 dg/min and most preferably at least 7 dg/min.
• the melt index is preferably at most 17.5 dg/min and more preferably at most 17 dg/min.
• the molecular weight of LDPE resins can be measured by two different methods: (1) the “conventional” or “relative” GPC method; and (2) the “absolute” method.
• the absolute method typically yields greater molecular weights than the conventional method for polymers with high levels of long-chain branching, such as LDPE resins.
• the conventional number average molecular weight (M n (conv) ) of the starting LDPE resin is preferably at least 7,000 g/mol, more preferably at least 12,000 g/mol and most preferably at least 13,000 g/mol.
• the conventional number average molecular weight (M n (conv) ) of the starting LDPE resin is preferably at most 30,000 g/mol, more preferably at most 25,000 g/mol, more highly preferably at most 18,000 g/mol and most preferably at most 16,000 g/mol.
• the conventional weight average molecular weight (M w (conv) ) of the starting LDPE resin is preferably at least 35,000 g/mol, more preferably at least 45,000 g/mol and most preferably at least 100,000 g/mol.
• the conventional weight average molecular weight (M w (conv) ) of the starting LDPE resin is preferably at most 300,000 g/mol and more preferably at most 180,000 g/mol.
• the starting LDPE resin has a conventional molecular weight distribution (M w (conv) /M n (conv) ) of at least 6.
• the conventional molecular weight distribution of the starting LDPE resin is preferably at least 7, more preferably at least 7.5 and most preferably at least 8.
• the conventional molecular weight distribution of the starting LDPE resin is preferably at most 13, more preferably at most 12 and most preferably at most 11.
• the absolute weight average molecular weight (M w (Abs) ) of the starting LDPE resin is preferably at least 100,000 g/mol and more preferably at least 270,000 g/mol.
• the absolute weight average molecular weight (M w (Abs) )) of the starting LDPE resin is preferably at most 750,000 g/mol, more preferably at most 500,000 g/mol and most preferably at most 450,000 g/mol.
• the ratio of absolute molecular weight to conventional molecular weight (M w (Abs) /M w (Conv) ) for the starting LDPE resin is preferably at least 1.5, more preferably at least 2.0 and most preferably at least 2.2.
• the ratio of absolute molecular weight to conventional molecular weight (M w (Abs) /M w (Conv) ) for the starting LDPE resin is preferably at most 5, more preferably at most 3.5 and most preferably at most 2.8.
• Long chain branching in polymers is also characterized by several different measurements.
• the measurements for branching that are described in the test methods below include: the branching index (g′), the long chain branching frequency (LCBf) and the GPC branching index (gpcBR).
• the long chain branching frequency (LCBf) of the starting LDPE resin is preferably at least 0.5, more preferably at least 1.0, and most preferably at least 1.2.
• the long chain branching frequency (LCBf) of the starting LDPE resin is preferably at most 5.0, more preferably at most 3.5, and most preferably at most 3.0.
• the GPC branching index (gpcBR) of the starting LDPE resin is preferably at least 0.5, more preferably at least 1.5 and most preferably at least 1.6.
• the GPC branching index (gpcBR) of the starting LDPE resin is preferably at most 6 and more preferably at most 4.
• the melt strength of the starting LDPE resin at 190° C. is preferably at most 20 cN, more preferably at most 10 cN, and most preferably at most 8 cN.
• the ratio of melt strength (in cN)/melt index (in dg/min) for the starting LDPE resin is preferably at least 0.1.
• the ratio of melt strength (cN)/melt index (dg/min) for the starting LDPE resin is preferably at most 10, more preferably at most 5 and most preferably at most 1.
• the gel content in the starting LDPE resin has been minimized.
• Gel content is conveniently measured by measuring the quantity of resin recovered through gel permeation chromatography (GPC recovery) as described in the Test Methods. Higher resin recovery corresponds to lower gel content.
• GPC recovery of the starting LDPE resin is preferably at least 95 percent, more preferably at least 97 percent, more highly preferably at least 99 percent and most preferably at least 99.5 percent. There is no maximum preferred GPC recovery; the GPC recovery may be essentially 100 percent.
• Viscosity ratio is a ratio of the viscosity of the resin under low-shear conditions (0.1 rad/s) divided by the viscosity of the resin under high shear conditions (100 rad/s), both at a temperature of 190° C.
• the viscosity ratio of the starting LDPE resin is preferably at least 1, more preferably at least 4 and most preferably at least 5.
• the viscosity ratio of the starting LDPE resin is preferably at most 20, more preferably at most 10 and most preferably at most 9.
• Tangent of the phase angle ⁇ is a viscoelastic measurement indicating the ratio of loss modulus (G′′) divided by storage modulus (G′) under low shear conditions (0.1 rad/s) at a temperature of 190° C.
• the starting LDPE resin preferably has a tan- ⁇ at 0.1 rad/s of at least 3, more preferably at least 5 and most preferably at least 6.
• the tan- ⁇ of the starting LDPE resin is preferably at most 50, more preferably at most 10, and most preferably at most 8.
• the starting LDPE resin may be a single polymer or a blend of two or more polymers. If it is a blend, the preferred embodiments above apply to the individual polymer components.
• the starting LDPE resin is a single polymer.
• the starting LDPE resin may optionally contain common additives, such as antistatic agents, color enhancers, dyes, lubricants, fillers, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, nucleators, slip agents such as erucamide, antiblock agents such as talc, and combinations thereof.
• additives in the starting LDPE resin do not interfere with long chain branch formation. More preferably, the starting LDPE resin contains essentially no additives.
• Starting LDPE resins are commercially available or can be made by known processes as described above in the Background Section.
• Starting LDPE resins are preferably made by free radical polymerization of ethylene monomer and optionally comonomers at a temperature of 180° C. to 350° C. and a pressure of from 14,500 psi to 58,000 psi (100-400 MPa).
• Polymerization is initiated by common free-radical initiators, such as organic peroxide initiators.
• Chain length can be controlled by adding chain transfer agents, such as butane, isobutane, butene, propylene, propionaldehyde, or methyl ethyl ketone.
• the reactor system may contain one or more autoclaves or high-pressure tubular reactors.
• starting LDPE resins in this invention have molecular weight distributions at the broader end of the range that is common for LDPE resins, and LDPE resins with broad molecular weight distribution are more commonly made in autoclave reactors. If a tubular reactor system is used, conditions should be adapted to produce the desired molecular weight distribution.
• the starting LDPE resin is preferably a powder, granule or pellet and is more preferably a pellet. Pellets generally have 10-60 pellets per gram.
• the starting LDPE resin is modified by irradiation with an electron beam.
• the combination of two free radicals forms long-chain branches.
• the additional long chain branches increase melt strength.
• the dosage of radiation should be high enough to initiate long chain branching, but low enough to avoid formation of highly cross-linked networks, which are gels.
• Sources for electron beam radiation are known and commercially available.
• the electron beam is preferably emitted from a linear electron beam accelerator.
• an electron beam is emitted from a heated cathode filament (typically tungsten).
• a linear accelerator the electrons emitted from the cathode are accelerated in an electric field applied between a cathode and an anode.
• the energy gain of the electron beam is proportional to the acceleration voltage.
• the energy is measured in eV (electron-volts), and accelerators up to 12 MeV are commercially available.
• the level of irradiation should be selected to achieve the following results:
• the starting LDPE resin preferably receives an average dosage of at least 0.2 MRad, more preferably at least 0.25 MRad, more highly preferably at least 0.4 MRad, and most preferably at least 0.45 MRad.
• the starting LDPE resin preferably receives an average dosage of at most 1.25 MRad, more preferably at most 1 MRad, and most preferably at most 0.8 MRad.
• the irradiation is too low, the desired melt-strength cannot be achieved in the modified LDPE resin. If the irradiation is too high, the melt index of the modified LDPE resin is too low, and the GPC recovery is too low.
• the linear electron beam accelerator preferably has the following characteristics.
• the electron beam penetration depth of the starting LDPE resin during irradiation is preferably shallow enough to allow all of the starting LDPE resin to receive a uniform desired dosage of electron beam radiation.
• the penetration depth of the electron beam depends upon the density of the LDPE and the beam energy (MeV).
• a 4.5 MeV beam is preferably used to irradiate the starting LDPE resin to a penetration depth of at most 6 cm, more preferably at most 4.5 cm and most preferably at most 3.5 cm, to ensure that all of the starting LDPE resin receives adequate and uniform exposure to the radiation.
• Irradiation preferably takes place in vacuum, air or inert atmosphere. Irradiation more preferably takes place in air.
• the e-beaming may be performed in a batch or continuous process. A continuous process where the starting LDPE resin is conveyed on a belt and exposed to an E-beam curtain is preferred.
• the preferred time of irradiation depends on the strength of the electron beam source (beam energy, current and beam power). Persons of ordinary skill can readily determine by experimentation the optimum time for irradiation based on the polymers and equipment they are working with.
• the product of the irradiation is a modified LDPE resin.
• the irradiation process does not materially change the following characteristics of the starting LDPE resin, and so the limits and preferred embodiments of the following characteristics of the modified LDPE resin after irradiation are the same as the limits and preferred embodiments for the starting PE resin: density, monomer and comonomer content, single polymer or blend of polymers, additive content, and physical form (powder, granule or pellet).
• the melt index (12) of the modified LDPE resin is preferably at least 1.0 dg/min, more preferably at least 1.5 dg/min, and most preferably at least 2 dg/min.
• the melt index of the modified LDPE resin is preferably at most 10 dg/min, more preferably at most 6 dg/min, and most preferably at most 3 dg/min.
• the melt index (12) of the modified LDPE resin is preferably at least 10% of the melt index of the starting LDPE resin and more preferably at least 20%.
• the melt index (I 2 ) of the modified LDPE resin is preferably at most 60% of the melt index of the starting LDPE resin and more preferably at most 30% of the melt index of the starting LDPE resin.
• the conventional number average molecular weight (M n (conv) ) of the modified LDPE resin is preferably at least 7,000 g/mol, more preferably at least 9,000 g/mol, and most preferably at least 13,000 g/mol.
• the conventional number average molecular weight (M n (Conv) ) of the modified LDPE resin is preferably at most 30,000 g/mol, more preferably at most 19,000 g/mol and most preferably at most 15,500 g/mol.
• the conventional weight average molecular weight (M w (conv) ) of the modified LDPE resin is preferably at least 45,000 g/mol, more preferably at least 100,000 g/mol and most preferably at least 120,000 g/mol.
• the conventional weight average molecular weight of the modified LDPE resin is preferably at most 400,000 g/mol, more preferably at most 300,000 g/mol and most preferably at most 265,000 g/mol.
• the conventional molecular weight distribution (M w (Conv) /M n (Conv) ) of the modified LDPE resin is at least 10.
• the conventional molecular weight distribution of the modified LDPE resin is preferably at least 12 and more preferably at least 14.
• the conventional molecular weight distribution of the modified LDPE resin is preferably at most 25, more preferably at most 20, and most preferably at most 18.
• the absolute weight average molecular weight (M w (Abs) ) of the modified LDPE resin is preferably at least 100,000 g/mol, more preferably at least 200,000 g/mol and most preferably at least 350,000 g/mol.
• the absolute weight average molecular weight of the modified LDPE resin is preferably at most 2,500,000 g/mol, more preferably at most 1,700,000 g/mol, and most preferably at most 1,250,000 g/mol.
• the ratio of the absolute weight average molecular weight to the conventional weight average molecular weight (M w (Abs) )/(M w (Conv) ) is preferably at least 1.6, more preferably at least 1.8 and most preferably at least 3.5.
• the ratio of the absolute weight average molecular weight to the conventional weight average molecular weight (M w (Abs) )/(M w (Conv) ) is preferably at most 12, more preferably at most 8, and most preferably at most 5.
• the long chain branching frequency (LCBf) of the modified LDPE resin is preferably at least 0.6, more preferably at least 1.0, more highly preferably at least 3.5, and most preferably at least 5.
• the long chain branching frequency (LCBf) of the modified LDPE resin is preferably at most 10, more preferably at most 8.0, and most preferably at most 7.6.
• a preferred goal of the modification process is to increase long chain branching in the starting LDPE resin.
• the long chain branching frequency (LCBf) of the modified LDPE resin is preferably at least 20% percent higher, as compared to the starting LDPE resin, more preferably at least 50% percent higher, and most preferably at least 100% higher.
• the long chain branching frequency (LCBf) of the modified LDPE resin is preferably at most 300% higher, as compared to the starting LDPE resin.
• the GPC branching index (gpcBR) of the modified LDPE resin is preferably at least 0.6, more preferably at least 0.8, more highly preferably at least 2.0 and most preferably at least 3.5.
• the GPC branching index (gpcBR) of the modified LDPE resin is preferably at most 12, more preferably at most 10 and most preferably at most 8.
• the modified LDPE resin preferably has a melt strength at 190° C. of at least 15 cN, more preferably at least 20 cN and most preferably at least 25 cN.
• the melt strength is preferably at most 35 cN and more preferably at most 32 cN.
• the melt strength at 190° C. of the modified LDPE resin is preferably at least 10 cN higher than the melt strength of the starting LDPE resin, more preferably at least 15 cN higher, more preferably at least 20 cN higher and most preferably at least 25 cN higher.
• the melt strength of the modified LDPE resin is preferably at most 45 cN higher than the melt strength of the starting LDPE resin, more preferably at most 35 cN higher and most preferably at most 30 cN higher.
• tubular reactor systems can produce LDPE resins at higher capacity and ethylene conversion rates, but LDPE resins made in an autoclave reactor system have higher melt strength.
• the starting LDPE resin is a product of a tubular reactor system; the modification process can nevertheless give it melt strength similar to or even superior to conventional LDPE resins made in an autoclave reactor system.
• the modified LDPE resin preferably has a viscosity ratio at 190° C. of at least 5, more preferably at least 9 and most preferably at least 12.
• the viscosity ratio is preferably at most 30, more preferably at most 25, and most preferably at most 18.
• the viscosity ratio of the modified LDPE resin is preferably at least 10% higher than the starting LDPE resin, more preferably at least 20% higher and most preferably at least 25% higher.
• the change in viscosity ratio indicates that the modified LDPE resin can form a more stable film at higher throughput rates in blown film production.
• the modified LDPE resin preferably has a tan- ⁇ at 190° C. and 0.1 rad/s of at least 1 and more preferably at least 2.
• the tan- ⁇ is preferably at most 10, more preferably at most 5, and most preferably at most 3.
• the tan- ⁇ of the modified LDPE resin is preferably at most 65 percent of the tan- ⁇ of the starting LDPE resin and more preferably at most 50 percent.
• the lower tan- ⁇ of the modified LDPE resins shows that they have improved elasticity.
• the ratio of melt strength (in cN)/melt index (in dg/min) for the modified LDPE resin is preferably at least 1, more preferably at least 3 and most preferably at least 10.
• the ratio of melt strength (cN)/melt index (dg/min) for the modified LDPE resin is preferably at most 30 and more preferably at most 20.
• the gel content of the modified LDPE resin is preferably less than 3 weight percent, more preferably less than 2.8 weight percent, more highly preferably less than 2 weight percent and most preferably less than 1 weight percent. In many cases, the gel content of the modified LDPE resin can be essentially 0 weight percent; the measured gel content can be less than or equal to the usual confidence limits of the test.
• the GPC recovery of the modified LDPE resin is preferably at least 95 percent, based on the weight of the modified LDPE resin, more preferably essentially 100 percent.
• the electron beam modification is not expected to reduce gel content, but the conditions of the modification are preferably selected to avoid or minimize formation of additional gels.
• One example of a preferred modified LDPE resin has the following properties:
• the modified polyethylene resin was irradiated as a powder or granule, then it is preferably extruded to form a pellet.
• the pellet may optionally include additives, such as antistatic agents, color enhancers, dyes, lubricants, fillers, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, nucleators, slip agents such as erucamide, antiblock agents such as talc, and combinations thereof; preferably, it does not include material quantities of additives.
• the powder, granule or pellets may be blended and/or coextruded with other resins, such as HDPE, LLDPE, or another LDPE, to make resin blends. It is well known to select and blend polyethylene resins having selected properties, so that the overall blend has desired properties.
• the powder, granule pellets or blends may be extruded to make extruded single layer or multilayer films and sheets, extruded coatings and extruded blow-molded articles and other products.
• This technology is well known and described briefly in the Background.
• Preferred uses for the modified LDPE resins and blends that contain them include blown and cast single layer and multi-layer films, stretched single layer and multi-layer films and extruded single-layer and multi-layer coatings.
• references to the physical and chemical properties of the LDPE resin mean the properties as they are measured by the following test methods.
• Density Density is measured according to ASTM D792, Method B.
• Melt Index Melt index, or I 2 , is measured according to ASTM D1238 at 190° C., 2.16 kg. Results are reported in decigrams per minute (dg/min).
• the extrudate passes through the wheels of the Rheotens located at 100 mm below the die exit and is pulled by the wheels downward at an acceleration rate of 2.4 mm/s 2 .
• the force (in cN) exerted on the wheels is recorded as a function of the velocity of the wheels (mm/s). Melt strength is reported as the plateau force (cN) before the strand breaks or has significant draw resonance.
• Irradiation Level The e-beam is calibrated using dosimetry films and measuring change in color. The irradiation level can then be calculated based on the electron beam energy, current and the belt speed.
• the gel content (insoluble fraction) produced by cross linking is determined by extracting with the solvent decahydronaphthalene. It is applicable to cross-linked ethylene plastics of all densities, including those containing fillers, and all provide corrections for the inert fillers present in some of those compounds. See ASTM D2765-16 , Standard Test Methods for Determination of Gel Content and Swell Ratio of Crosslinked Ethylene Plastics , ASTM International, West Conshohocken, PA, 2016, www.astm.org.
• Vinyl Content The vinyl content of LDPE is determined by 1H NMR spectroscopic methods, which are described in Busico, V., et al., Macromolecules, 2005, 38, 6988 and U.S. Pat. No. 8,916,667 from col 11, line 35 to col. 12, line 15.
• Samples were prepared by adding ⁇ 0.1 to 0.2 g of sample to 3.25 g of 50/50 by weight 1,1,2,2-tetrachlorethane-d2/perchloroethylene (TCE/PCE) containing 0.001 M Cr(AcAc) 3 and about 75 ppm butylated hydroxytoluene (BHT), in a Norell 1001-7 10 mm NMR tube.
• TCE/PCE 1,1,2,2-tetrachlorethane-d2/perchloroethylene
• BHT butylated hydroxytoluene
• 1H NMR was performed on a Bruker AVANCE 600 MHz spectrometer equipped with a Bruker high-temperature CryoProbe at a sample temperature of 120° C. Spectra were acquired with ZG pulse, 1.8 s AQ, 64 or 128 scans with a relaxation delay of 14 s.
• the spectra were referenced to the residual proton signal of TCE at 6.0 ppm.
• the total polymer integral from about ⁇ 0.5 to 2.5 ppm was set to an arbitrary value, for example, 2000.
• the corresponding integrals for unsaturations (cis- and trans-vinylenes from about 5.40 to 5.60 ppm, trisubstituted from about 5.16 to 5.35 ppm, vinyl from about 5.0 to 5.15 ppm, and vinylidene from about 4.75 to 4.85 ppm) were obtained.
• the BHT —OH signal at about 4.9 ppm was not included in the integral areas.
• the integral of the whole polymer is divided by 2 to obtain the total polymer carbons, 1000 in this example.
• the unsaturated group integrals divided by the corresponding number of protons contributing to that integral represent the moles of each type of unsaturation per 1000 moles of total polymer carbons. This is referred to as unsaturated groups per 1000 carbons.
• Samples for 13C NMR were prepared by adding approximately 3 g of 1,1,2,2-tetrachloroethane (TCE) containing 25 wt % TCE-d2 and 0.025 M Cr(AcAc) 3 , to about 0.25 g polymer sample, in a 10 mm NMR tube. Oxygen was removed from the sample by purging the headspace with nitrogen. The samples were then dissolved and homogenized by heating the tube and its contents to 120-140° C. using a heating block and vortex mixer. Each dissolved sample was visually inspected to ensure homogeneity. Samples were thoroughly mixed immediately prior to analysis and were not allowed to cool before insertion into the heated NMR sample holders.
• TCE 1,1,2,2-tetrachloroethane
• the “C6+” value is a direct measure of C6+ branches in LDPE, where the long branches are not distinguished from “chain ends.”
• Branching Type and 13C NMR integral ranges used for quantitation Branch Type Peak(s) integrated Identity of the integrated carbon peak(s) 1,3 diethyl about 10.5 to 11.5 ppm 1,3 diethyl branch methyls C2 on quaternary about 7.5 to 8.5 ppm 2 ethyl branches on a quaternary carbon, carbon methyls C4 about 23.3 to 23.5 ppm Second CH 2 in a 4-carbon branch, counting the methyl as the first C C5 about 32.60 to 32.80 ppm Third CH 2 in a 5-carbon branch, counting the methyl as the first C C6+ about 32.1 to 32.3 ppm The third CH 2 (counting the methyl as the first C) in any branch of 6 or more carbons in length C4+ about 38.2 ppm The CH carbon for branches or segments of 4 or more carbons in length, when said branch is at least about 4 to 5 carbons distant from any other branch
• GPC Gel Permeation Chromatography
• the chromatographic system consists of a PolymerChar GPC-IR (Valencia, Spain) high temperature GPC chromatograph equipped with an internal IR5 infra-red detector (IR5), a Precision Detectors (Now Agilent Technologies) 2-angle laser light scattering (LS) detector Model 2040, and an internal 4-capillary viscometer. For all light scattering measurements, the 15 degree angle is used.
• the columns in the GPC chromatograph are four Agilent “Mixed A” 30 cm 20-micron linear mixed-bed columns and a 20-um pre-column.
• the autosampler oven compartment is at 160° Celsius and the column compartment was set at 150° Celsius.
• Calibration of the GPC column set is performed with 21 narrow molecular weight distribution polystyrene standards with molecular weights ranging from 580 g/mol to 8,400,000 g/mol and were arranged in 6 “cocktail” mixtures with at least a decade of separation between individual molecular weights.
• the standards are purchased from Agilent Technologies.
• the polystyrene standards are prepared at 0.025 grams in 50 milliliters of solvent for molecular weights equal to or at least 1,000,000 g/mol, and 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000 g/mol.
• the polystyrene standards are dissolved at 80 degrees Celsius with gentle agitation for 30 minutes.
• the polystyrene standard peak molecular weights are converted to polyethylene molecular weights using Equation 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)):
• A has a value of 0.4315 and B is equal to 1.0.
• a fifth order polynomial is used to fit the respective polyethylene-equivalent calibration points. (A small adjustment to A (from approximately 0.3950 to 0.440) was made to correct for column resolution and band-broadening effects such that such that linear homopolymer polyethylene standard is obtained at 120,000 Mw).
• the total plate count of the GPC column set is performed with decane (prepared at 0.04 g in 50 milliliters of TCB.)
• the plate count (Equation 2) and symmetry (Equation 3) are measured on a 200 microliter injection according to the following equations:
• LDPE Samples are prepared as follows: The chromatographic solvent is 1,2,4 trichlorobenzene containing 200 ppm of butylated hydroxytoluene (BHT). The solvent source is nitrogen sparged. Samples are prepared in a semi-automatic manner with the PolymerChar “Instrument Control” Software, wherein the samples are weight-targeted at 1 mg/ml, and the solvent is added to a pre nitrogen-sparged septum-capped vial, via the PolymerChar high temperature autosampler. The samples are dissolved for 2 hours at 160° Celsius under low orbital shaking. The injection volume into the columns is 200 microliters, and the flow rate was 1.0 milliliters/min.
• BHT butylated hydroxytoluene
• a flowrate marker (decane) is introduced into each sample via a micropump controlled with the PolymerChar GPC-IR system.
• This flowrate marker (FM) is used to linearly correct the pump flowrate (Flowrate(nominal)) for each sample by retention volume (RV) alignment of the respective decane peak within the sample (RV(FM Sample)) to that of the decane peak within the narrow standards calibration (RV(FM Calibrated)). Any changes in the time of the decane marker peak are then assumed to be related to a linear-shift in flowrate (Flowrate(effective)) for the entire run.
• a least-squares fitting routine is used to fit the peak of the flow marker concentration chromatogram to a quadratic equation.
• the first derivative of the quadratic equation is then used to solve for the true peak position.
• the effective flowrate (with respect to the narrow standards calibration) is calculated as Equation 4.
• the flow marker peak is processed via the PolymerChar GPCOneTM Software. Acceptable flowrate correction is such that the effective flowrate should be within +/ ⁇ 1% of the nominal flowrate.
• Flowrate(effective) Flowrate(nominal)*(RV(FM Calibrated)/RV(FM Sample)) (4)
• Mn (conv) and Mw (conv) are calculated according to Equations 5-6, using PolymerChar GPCOneTM software, the baseline-subtracted IR chromatogram at each equally-spaced data collection point (i), and the polyethylene equivalent molecular weight obtained from the narrow standard calibration curve for the point (i) from Equation 1.
• Mn ⁇ ( conv ) ⁇ i ⁇ IR i ⁇ i ⁇ ( IR i / M polyet ⁇ hylene i ) ( 5 )
• Mw ⁇ ( conv ) ⁇ i ⁇ ( IR i * M polyet ⁇ hylene i ) ⁇ i ⁇ IR i ( 6 )
• the absolute weight average molecular weight (M w(Abs) ) is obtained (using GPCOneTM) from the area of the Light Scattering (LS) integrated chromatogram (factored by the light scattering constant) divided by the mass recovered from the mass constant and the mass detector (IR5) area at each elution volume.
• the overall injected concentration, used in the determination of the molecular weight is obtained from the mass detector area and the mass detector constant, derived from a suitable linear polyethylene homopolymer, or one of the polyethylene standards of known weight-average molecular weight.
• the mass detector response (IR5) and the light scattering constant (determined using GPCOneTM) is determined from a linear polyethylene standard with a molecular weight in excess of about 50,000 g/mole.
• the calculated molecular weights (using GPCOneTM) were obtained using a light scattering constant, derived from one or more of the polyethylene standards mentioned below, and a refractive index concentration coefficient, dn/dc, of 0.104.
• the viscometer calibration (determined using GPCOneTM) can be accomplished using the methods described by the manufacturer, or, alternatively, by using the published values of suitable linear standards, such as Standard Reference Materials (SRM) 1475a (available from National Institute of Standards and Technology (NIST)).
• SRM Standard Reference Materials
• a viscometer constant (obtained using GPCOneTM) is calculated which relates specific viscosity area (DV) and injected mass for the calibration standard to its intrinsic viscosity (IV).
• the chromatographic concentrations are assumed low enough to eliminate addressing 2 nd viral coefficient effects (concentration effects on molecular weight).
• the absolute weight average molecular weight (M w (Abs)) is obtained (using GPCOneTM) from the area of the Light Scattering (LS) integrated chromatogram (factored by the light scattering constant) divided by the mass recovered from the mass constant and the mass detector (IR5) area at each elution volume.
• M w (Abs) The absolute weight average molecular weight (M w (Abs)) is obtained (using GPCOneTM) from the area of the Light Scattering (LS) integrated chromatogram (factored by the light scattering constant) divided by the mass recovered from the mass constant and the mass detector (IR5) area at each elution volume.
• the molecular weight and intrinsic viscosity responses are extrapolated at chromatographic ends where signal to noise becomes low (using GPCOneTM).
• the viscometer calibration (determined using GPCOneTM) can be accomplished using the methods described by the manufacturer, or, alternatively, by using the published values of suitable linear standards, such as Standard Reference Materials (SRM) 1475a (available from National Institute of Standards and Technology (NIST)).
• SRM Standard Reference Materials
• a viscometer constant (obtained using GPCOneTM) is calculated which relates specific viscosity area (DV) and injected mass for the calibration standard to its intrinsic viscosity (IV).
• the gpcBR branching index is determined using data from the light scattering, viscosity, and concentration detectors as described previously. Baselines are subtracted from the light scattering, viscometer, and concentration chromatograms. Integration windows are set to ensure integration of all of the low molecular weight retention volume range in the light scattering and viscometer chromatograms that indicate the presence of detectable polymer from the infrared (IR5) chromatogram.
• IR5 infrared
• Linear polyethylene standards are used to establish polyethylene and polystyrene Mark-Houwink constants. Upon obtaining the constants, the two values are used to construct two linear reference conventional calibrations for polyethylene molecular weight and polyethylene intrinsic viscosity as a function of elution volume, as shown in Equations (7) and (8):
• [ ⁇ ] PE K PS ⁇ MW PS ⁇ +1 /MW PE (8)
• sample intrinsic viscosities are also obtained independently using Equation (9).
• This area calculation offers more precision, because, as an overall sample area, it is much less sensitive to variation caused by detector noise and 3D-GPC settings on baseline and integration limits. More importantly, the peak area calculation is not affected by the detector volume offsets.
• the high-precision sample intrinsic viscosity (IV) is obtained by the area method shown in Equation (9):
• ⁇ spi stands for the specific viscosity as acquired from the viscometer detector.
• the light scattering elution area for the sample polymer is used to determine the molecular weight of the sample.
• the viscosity detector elution area for the sample polymer is used to determine the intrinsic viscosity (IV or [ ⁇ ]) of the sample.
• the molecular weight and intrinsic viscosity for a linear polyethylene standard sample are determined using the conventional calibrations (“cc”) for both molecular weight and intrinsic viscosity as a function of elution volume, per Equations (10) and (11):
• Equation (11) is used to determine the gpcBR branching index:
• gpcBR [ ( [ ⁇ ] cc [ ⁇ ] ) ⁇ ( M w M w , cc ) ⁇ PE - 1 ] ( 11 )
• [ ⁇ ] is the measured intrinsic viscosity
• [ ⁇ ]cc is the intrinsic viscosity from the conventional calibration
• Mw is the measured weight average molecular weight
• Mw,cc is the weight average molecular weight of the conventional calibration.
• the weight average molecular weight by light scattering (LS) is commonly referred to as “absolute weight average molecular weight” or “M w (Abs) .”
• the Mw,cc from Equation (6) using conventional GPC molecular weight calibration curve (“conventional calibration”) is often referred to as “polymer chain backbone molecular weight,” “conventional weight average molecular weight,” and “Mw (conv).”
• gpcBR calculated from Equation (11) will be close to zero, since the values measured by LS and viscometry will be close to the conventional calibration standard.
• gpcBR will be higher than zero, especially with high levels of long chain branching, because the measured polymer molecular weight will be higher than the calculated Mw,cc, and the calculated IVcc will be higher than the measured polymer IV.
• the gpcBR value represents the fractional IV change due the molecular size contraction effect as the result of polymer branching.
• a gpcBR value of 0.5 or 2.0 would mean a molecular size contraction effect of IV at the level of 50% and 200%, respectively, versus a linear polymer molecule of equivalent weight.
• LCB f (LCB1000C) (in long-chain branches per 1000 carbon atoms) is calculated for each polymer sample by the following procedure:
• LDPE resins are obtained from commercial stocks of pelleted resin: LDPE 722, LDPE 4016, AGILITYTM EC 7080, LDPE 780E, LDPE 993I, and LDPE 9551. All resins are available from Dow, Inc. The resins are additive-free, except LDPE 993I contains slip-agent. Initial Properties of each resin are measured using the Test Methods described above, and the results are listed in Table 2.
• Modified LDPEs are produced by irradiating the starting LDPEs to a pre-determined dosage (up to 1.15 MRad) using a DYNAMITRON linear electron beam accelerator in air.
• the operating parameters of the electron-beam accelerator are: an energy range of 4.5 MeV, a beam power over the whole energy range of 150 kW, a beam energy spread of +/ ⁇ 10 percent and an average current of 30 milliamps (mA).

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